JP2022160687A - Polyester polyol compositions containing hf0-1336mzzm (z) - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide blends, polyol premix compositions, methods of forming such compositions, foamable compositions using the premix compositions, methods of preparing foams containing the premix compositions, and foams made using the premix compositions.

SOLUTION: A polyol premix composition includes a polyester polyol, a halogenated olefin blowing agent, and a distribution-enhancing component that is one or more of alcohols, glycols, ethers, acetals, benzenes, ketones, chlorinated solvents, carbonates, solvents and surfactants. In the polyol premix composition, the blowing agent, the polyester polyol and the distribution-enhancing component form a substantially uniform composition.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority benefit of U.S. Provisional Application No. 62/366,437, filed July 25, 2016. /631,70
9, the contents of which are incorporated herein by reference.

The present invention relates to polyurethane and polyisocyanurate foams and methods for their preparation. More specifically, the present invention provides rigid, semi-rigid, and flexible polyurethane and polyisocyanurate foams and cis-1,1,1,4,4,4-hexafluorobut-2-ene ( Halogenated olefins as blowing agents, including HFO-1336mzzm(Z)), and methods for their preparation using polyester polyols.

A class of foams known as low-density, rigid, semi-rigid, and flexible polyurethane or polyisocyanurate foams are used in roofing systems, building panels, building envelope insulation, refrigerators and freezers, seat cushions, mattresses, shoes. Useful in a wide range of insulating applications such as bottoms, packaging materials, etc. A key factor in the large-scale commercial acceptance of rigid polyurethane foams is their ability to provide a good balance of properties. Rigid, closed-cell polyurethane and polyisocyanurate foams are known to provide excellent thermal insulation, excellent fire resistance, and excellent structural properties at reasonably low densities. Semi-flexible and flexible polyurethane foams are known to provide excellent cushioning and energy absorption properties. The foam industry has in the past used certain liquid fluorocarbon materials as blowing agents because of their ease of use under typical processing conditions. Certain fluorocarbons are not only capable of acting as blowing agents due to their volatility, but in the case of closed cell foams, they are entrained in the closed cell structure of rigid foams and have a low thermal effect in rigid urethane foams. It is also the main cause of conductivity. The use of certain fluorocarbon materials as preferred commercial expanding or blowing agents in insulating foam applications is based in part on the resulting k-factor associated with the foam produced. The k-factor is the rate of transfer of heat energy by conduction through a square foot of homogeneous material 1 inch thick in 1 hour with a difference of 1°F across the two surfaces of the material perpendicularly. Defined. Since the use of many closed-cell polyurethane-type foams is based in part on the thermal insulation properties of the foam, it is advantageous to identify materials that produce lower k-factor foams. In the case of flexible polyurethane foams, certain fluorocarbon-containing physical blowing agents are used to reduce the density of these foams to levels difficult to achieve using water alone.

It is known in the art to produce polyurethane and polyisocyanurate foams by reacting polyisocyanates with polyols in the presence of blowing agents, catalysts, surfactants, and optionally other ingredients. . For many applications, the blowing agent should be distributed substantially homogeneously in the polyol component. The heat generated when the polyisocyanate reacts with the polyol volatilizes the blowing agent contained in the liquid mixture and forms foam therein. As the polymerization reaction proceeds, the liquid mixture becomes a polymeric cellular solid, encapsulating the blowing agent within the foam cells in the closed cell foam. In many applications, if no surfactant is used in the foamable composition, the foam will simply pass through the liquid mixture without forming a foam, or it will be too large to render a rigid foam unusable. Forms a foam with irregular cells. Also, if the blowing agent is not distributed substantially uniformly throughout the foamable composition during foaming, an irregular and inconsistent foam will form.

Suitable blowing agents include certain fluorocarbons, chlorocarbons, chlorofluorocarbons, hydrohaloolefins, hydrocarbons, ethers, esters, aldehydes, ketones, acetals, organic acids, atmospheric gases, gases through decomposition or chemical reactions, Examples include materials that produce CO2, such as but not limited to water, formic acid, and azodicarbonamide, and mixtures of two or more thereof. Preferred blowing agents have a low global warming potential. These blowing agents include hydrofluoroolefins.
efin, HFO) (hydrochlorofluoroolefin
There are certain hydrohaloolefins, including oroolefins, also known as HFCO. Of particular interest are trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), cis-1,1,1,4,4,4-hexafluorobut-2-ene (HFO -1336mzz(Z)), and trans-1-chloro-3,3,
3-trifluoropropene (HFO-1233zd(E)). Processes for the production of 1,3,3,3-tetrafluoropropene are disclosed in US Pat. Nos. 7,230,146 and 7,189,884. Processes for the production of 1-chloro-3,3,3-trifluoropropene are disclosed in US Pat. Nos. 6,844,475 and 6,403.
, 847. As used herein, the notation "(E)" refers to the trans isomer of the molecule and "(Z)" refers to the cis isomer.

Providing the components for polyurethane or polyisocyanurate foams in a pre-blended formulation is convenient in many applications. Most typically, the foam formulation is pre-blended into two components. The polyisocyanate and any isocyanate-compatible raw materials comprise a first component, commonly referred to as the "A" component. Polyols or mixtures of polyols, surfactants, catalysts, blowing agents, and other isocyanate-reactive and non-reactive components comprise the second component, commonly referred to as the "B" component. Thus, polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B subcomponents, either by hand mixing for small scale preparations, and preferably by mechanical mixing techniques. to form blocks, slabs, laminates, cast-in-place panels, flexible foams, soles and other articles, blown foams, flosses, molded articles, and the like. Optionally, all or part of the blowing agent can be added to the mix head or reaction site along with other ingredients such as flame retardants, colorants, auxiliary blowing agents, and other polyols. Most conveniently, however, they are all incorporated into one B component.

In order for the physical blowing agent to obtain a foam with uniform density and cell structure, the blowing agent is distributed substantially uniformly, for example by being dissolved, dispersed and/or emulsified in the polyol,
It should form a substantially homogeneous blend of polyol and blowing agent.
The mixture should remain homogeneous and not foamy if agitated during shipping. There are many types of polyols that are used to make polyurethane or polyisocyanurate foams. Most polyurethane or polyisocyanurate foams are prepared from blends of polyols with different structures and properties. Polyols used directly have a direct impact on the physical properties of polyurethane or polyisocyanurate foams. For each polyurethane or polyisocyanurate foam application, the choice of polyol is different as is the concentration of blowing agent. Most of the polyols used fall into two classes, polyethers and polyesters. The structure of each class of polyol is different. The use of polyester polyols is important for many applications. One of the polyols used in some formulations
00% is polyester polyol. An important consideration in formulation development is the temperature range in which the blend is formed, stored, and transported (eg, -20°C to 50°C) and/or the temperature range in which the foam is formed (eg, 10°C to 55°C). C.), the blowing agent can be uniformly distributed in the polyol blend. In addition to being uniform, the blend should not be foamy.

Applicants have found that certain polyols do not readily form uniform distributions with certain blowing agents under the conditions under which they are conventionally used and in the presence of other materials conventionally used. came to understand. Blending can cause foaming, shipping and use problems. The inclusion of certain materials in the blend overcomes these shortcomings and is achieved when the blowing agent is otherwise poorly distributed and not substantially uniformly distributed in the polyol. Applicants have found that the degree of uniform distribution can be improved or enhanced.

One aspect of the present invention relates to a polyol premix composition, wherein the polyol premix composition is a blowing agent comprising (a) a polyester polyol and (b) a halogenated olefin blowing agent, preferably a C3 or C4 halogenated olefin. and even more preferably HF
a blowing agent comprising cis-1,1,1,4,4,4-hexafluorobut-2-ene, also referred to as O-1336mzzm(Z); and (c) a haloolefin blowing agent in a polyester polyol. at least one that enables uniform distribution and/or improves the uniformity of the distribution;
and one distribution-enhancing component. As used herein, distribution-enhancing components selected in accordance with the present invention may also be referred to herein for convenience as "compatibilizers." One indication that a substantially uniform distribution of blowing agent has not been achieved is preferably phase separation after attempted blending/mixing of the components, conditions such as those described in the Examples herein. Visual observation below. Conversely, one indication in preferred embodiments of the presence of a substantially uniform distribution is
Preferably, visual observation under conditions such as those described in the Examples herein of a substantially consistent liquid phase with no signs of phase separation.

Other aspects of the invention include blends, methods of preparing foamable compositions, foamable compositions, and foams.

One aspect of the present invention is the selection of organic compatibilizers, preferably organic hydroxy-containing compounds having from 1 to 40 carbon atoms, even more preferably from 1 to 25 carbon atoms. In certain preferred embodiments, acyclic alcohols having 1 to 10 carbon atoms, cyclic alcohols having 6 to 40 carbon atoms, alkylphenols and alkylphenol ethoxylates, dipropylene glycol, diisopropylene glycol, Dipropylene glycol methyl ether, methylal (methylene dimethyl ether), ethylene glycol mono-
butyl ether, 1,3-diisopropenylbenzene, isopropenylbenzene, acetone, methyl ethyl ketone, trans-1,2-dichloroethylene, 2-chloropropane,
trans-1-chloro-3,3,3-trifluoropropene, methyl formate, propylene carbonate, dioctyl phthalate, toluene, tris(1-chloro-2-propyl) phosphate, and any two thereof It is selected from the group consisting of the above combinations.

In certain aspects, the present invention provides a distribution enhancing component, preferably a distribution enhancing component as identified in the preceding paragraph or as described elsewhere herein, and (a)
Including blends containing either halogenated olefin blowing agents or (b) polyester polyols. In a preferred embodiment, the halogenated blowing agent is cis-1,1,1,4,4,4
may comprise or consist essentially of or consist of -hexafluorobut-2-ene. Preferably, the blend is formed as a substantially homogeneous blend or mixture of components, and even more preferably, the blowing agent or polyester polyol, whichever is present, is solvated by and/or substantially uniformly dispersed in and/or substantially uniformly emulsified therein; alternatively, the compatibilizer is solvated by the blowing agent or the polyester polyol (whichever is present); and/or substantially uniformly dispersed therein and/or substantially uniformly emulsified therein. In such embodiments, the solution/dispersion/emulsion is stored in a sealed container at a storage temperature under expected ambient temperature conditions, preferably for a period of 4 months, more preferably for a period of 6 months, and during storage. It is also highly preferred that it is stable on storage, more preferably for a period of one year. In certain preferred embodiments, stable storage exists according to the present invention at temperatures from about -20°C to about 55°C.

Another aspect of the invention is a polyol premix composition. In one embodiment, the polyol premix composition comprises at least one polyester polyol and cis-1,1
,1,4,4,4-hexafluorobut-2-ene blowing agent and a distribution enhancing component of the present invention, preferably an acyclic alcohol having 1 to 10 carbon atoms, 6 to 40 carbons. Atom-containing cyclic alcohols, alkylphenols and alkylphenol ethoxylates, dipropylene glycol, diisopropylbenzene, dipropylene glycol methyl ether, methylal, ethylene glycol mono-butyl ether, 1,3-diisopropylbenzene, isopropylbenzene, 1,3- diisopropenylbenzene, isopropenylbenzene, acetone, methyl ethyl ketone, trans-1,2-dichloroethylene, 2
-chloropropane, trans-1-chloro-3,3,3-trifluoropropene, methyl formate, propylene carbonate, dioctyl phthalate, toluene, tris(1-chloro-2
-propyl), and a compatibilizer selected from the group consisting of combinations of any two or more thereof, wherein the blowing agent and the distribution enhancing component preferably comprise By being substantially uniformly dispersed in the polyol and/or emulsified therein and/or solvated thereby, it is substantially uniformly distributed as a blend or in the polyol premix.

Another aspect of the invention is a method of forming a polyol premix composition. In one embodiment, the method comprises: (a) a polyester polyol; and (b) cis-1,1,1,4,4,
a blowing agent comprising, even more preferably comprising, even more preferably consisting essentially of, at least about 50% by weight of 4-hexafluorobut-2-ene; formula alcohols, cyclic alcohols having 6 to 40 carbon atoms, alkylphenols and alkylphenol ethoxylates, ethylene glycol, dipropylene glycol, diisopropyl ether, dipropylene glycol methyl ether, methylal, ethylene glycol mono-butyl ether, 1, 3-diisopropylbenzene, isopropylbenzene, 1,3-diisopropenylbenzene, isopropenylbenzene, acetone, methyl ethyl ketone, trans-1,2-dichloroethylene, 2-chloropropane, trans-1-chloro-3,3,3-tri A distribution enhancing configuration selected from the group consisting of fluoropropene, methyl formate, propylene carbonate, dioctyl phthalate, toluene, tris(1-chloro-2-propyl) phosphate, and combinations of any two or more thereof. The blowing agent and the distribution enhancing component are preferably substantially uniformly dispersed and/or emulsified in the polyol and/or whereby the blowing agent and the distribution enhancing component are Combining a distribution-enhancing component, (d) an amine catalyst, and (e) a silicone surfactant, which are solvated to distribute substantially uniformly in the polyol.

Another aspect of the invention is a foamable composition. In one embodiment, the foamable composition comprises a mixture of an organic polyisocyanate and a polyol premix composition according to the invention.

Another aspect of the invention is a method of preparing a polyurethane or polyisocyanurate foam. In one embodiment, the method includes reacting an organic polyisocyanate with a polyol premix composition according to the invention.

Another aspect of the present invention is a foam produced according to a method utilizing the compatibilizer blend, and/or polyol premix, and/or foamable composition of the present invention.

HFO-1336mzzm(Z) is a recently developed hydrohaloolefin. HFO-13 uniformly distributed in various polyester polyols, as discussed below
1,1,1,3,3-pentafluoropropane (HFC-245fa) and trans-1-chloro-3,3,3-trifluoropropene (HFO) at different concentrations and temperatures. -1233zd(E)) compared to the performance of two other commonly used blowing agents. The ability of HFO-1336mzzm(Z) to achieve uniform distribution varied significantly with polyester polyol used, concentration, and temperature, and in the absence of the invention described herein. , HFO-1336mzzm(Z) was surprisingly found to be poorly distributed at best in many commonly used polyester polyols. This severely limits its use as a substantial constituent of blowing agents in polyurethane or polyisocyanurate foams. HFO-123
Applicants find that 3zd(E) appears to have superior ability to provide uniform distribution with some polyol esters compared to HFO-1336mzzm(Z), but HFO-1336mzzm(Z) It is possible to achieve improved or enhanced distribution of blowing agents containing 1233zd(E) and less solution foam, and such blowing agents are used in accordance with the teachings contained herein. Applicants also found that Halogenated olefins, more preferably C3 and C4 halogenated olefins such as HFO-1336mzzm(Z)
Applicants have also surprisingly found that certain compounds can enhance the degree to which is uniformly distributed in certain polyester polyols used in polyol premix compositions. rice field. As noted above, these compounds and blends of compounds are referred to herein as compatibilizers. The compatibilizer is preferably a halogenated olefin,
For example, HFO-1336mzzm(Z), and/or a polyester polyol, and preferably both solvated by and/or dispersed therein and/or emulsified therein. Further, the uniform distribution thus formed is preferably a stable, substantially uniform distribution of the blowing agent in the polyol. As used herein, a stable substantially uniform distribution means that the substantially uniform distribution is stored for a period of 4 months, preferably for a period of 6 months, and even more preferably for a period of 1 year. C. means maintained at at least one temperature, and preferably over the entire temperature range of about -20.degree. C. to about 55.degree. In preferred embodiments, the stable, substantially uniform distribution comprises a stable solution and/or dispersion and/or emulsion of the blowing agent in the polyol. Desirably, the compatibilizer can be used with a wide variety of polyester polyols over a wide range of concentrations, and storage stability is
It is shown over at least the preferred temperature ranges described herein.

Desirably, the compatibilizer can be combined with HFO-1336mzzm(Z), or polyester polyol, or a mixture of HFO-1336mzzm(Z), polyester polyol, and any other components in the polyol premix composition. .

Various materials were studied to determine their effectiveness as compatibilizers in various polyols. The distribution enhancing component typically has 1-40 carbon atoms. In some embodiments, the distribution enhancing component has one or more hydroxyl groups. Distribution enhancing components include alcohols, glycols, ethers, acetals, benzenes, ketones, chlorinated solvents,
It may include many one of carbonates, solvents, and surfactants.

Preferred compatibilizers are acyclic alcohols having 1 to 10 carbon atoms, cyclic alcohols having 6 to 40 carbon atoms (preferably about 6 to about 15 carbon atoms), alkylphenols and alkylphenols. Ethoxylate, Ethylene Glycol, Dipropylene Glycol, Diisopropyl Glycol, Dipropylene Glycol Methyl Ether, Methylal, Ethylene Glycol Mono-Butyl Ether, 1,3-Diisopropylbenzene, Isopropylbenzene, 1,3-Diisopropenylbenzene, Isopropenyl Benzene, acetone, methyl ethyl ketone, trans-1,2-dichloroethylene, 2-chloropropane, trans-1-chloro-3,3,3-trifluoropropene, methyl formate, propylene carbonate, dioctyl phthalate, toluene, tris phosphate ( 1-chloro-2-propyl) (tris(1-chloro-2-propyl) phosphate, TCPP)
, and combinations of any two or more thereof.

Preferred acyclic alcohols may be straight or branched chain and preferably have 1 to 10 carbon atoms, or 1 to 9 carbon atoms, or 1 to 8 carbon atoms, or 1 to 7 1 to 6 carbon atoms, or 1 to 5 carbon atoms, or 2 to 5 carbon atoms, or 2 to 4 carbon atoms. Preferred acyclic alcohols are monofunctional alcohols.
Preferred monofunctional alcohols are ethanol, methanol, isopropanol, n-butanol, 2-propanol, 1-pentanol, 3-methyl-2-butanol and 2-methyl-1-propanol.

Preferred cyclic alcohols preferably have 6 to 40 carbon atoms, or 6 to 35 carbon atoms, or 6 to 30 carbon atoms, or 6 to 25 carbon atoms, or 6 to 20 carbon atoms. atoms, or 6 to 15 carbon atoms, or 6 to 14 carbon atoms, or 6 to 12 carbon atoms, or 6 to 10 carbon atoms, or 6 to 9 carbon atoms, or 6 to It has 8 carbon atoms.

In some embodiments, the compatibilizer is an alkylphenol, in preferred embodiments
Examples include alkylphenol alkoxylates including alkylphenol ethoxylates. Certain preferred embodiments include, but are not limited to, nonylphenol and nonylphenol ethoxylates.

One aspect of the invention provides a blend of compatibilizer and either HFO-1336mzzm(Z) or polyester polyol. Another aspect is the compatibilizer, HFO-1336
A polyol premix composition is provided comprising mzzm(Z) and a polyester polyol. Other aspects are a method of preparing a polyol premix composition and a method of preparing a polyurethane or polyisocyanurate foam using the polyol premix composition and a foamable composition using the polyol premix composition. I will provide a.

One aspect of the invention is a compatibilizer blend. In some embodiments, the compatibilizer blend comprises a compatibilizer according to the present invention and HFO-1336mzzm(Z). A compatibilizer blend can include a compatibilizer and a polyester polyol. The compatibilizer blend can optionally contain one or more compatibilizers.

The compatibilizer is optionally from about 0.5 wt% to about 10 wt%, or about 0.5 wt% based on the amount of compatibilizer and blowing agent, or the amount of compatibilizer and polyester polyol. to about 9 wt%, or from about 0.5 wt% to about 8 wt%, or from about 0.5 wt% to about 7 wt%, or from about 0.
5% to about 6%, or from about 0.5% to about 5%, or from about 1% to about 10%, or from about 2% to about 10%, or from about 3% to About 10 wt%, or about 4 wt%~
It can be present in an amount of about 10% by weight.

Another aspect of the invention is a polyol premix composition. The polyol premix composition comprises a polyester polyol and a halogenated olefin blowing agent, preferably a C3 or C4 halogenated olefin, even more preferably cis-1,1,1,4,4,4-hexafluorobut-2- It contains an en-blowing agent and a compatibilizer. the blowing agent, or the polyester polyol, or both together form a stable, substantially homogeneous combination of components;
In preferred embodiments, this is achieved by combining the components to form stable solutions, dispersions, and/or emulsions.

The compatibilizer can be present in an amount of at least about 1.7% by weight of the polyol premix composition.

With respect to the polyol premix composition, the compatibilizer is from about 0.01 wt% to about 10 wt%, or from about 0.01 wt% to about 9
% by weight, or from about 0.01% to about 8%, or from about 0.01% to about 7%, or from about 0.01% to about 6%, or from about 0.01% about 5 wt%, or about 0.05 wt% to about 10 wt%, or about 0.05 wt% to about 9 wt%, or about 0.05 wt% to about 8 wt%
% by weight, or from about 0.05% to about 7%, or from about 0.05% to about 6%, or from about 0.05% to about 5%, or from about 0.1% about 10% by weight, or from about 0.1% to about 9%, or from about 0.1% to about 8%, or from about 0.1% to about 7%;
or about 0.1 wt% to about 6 wt%, or about 0.1 wt% to about 5 wt%, or about 0.3 wt% to about 10 wt%, or about 0.3 wt% to about 9 wt% %, or from about 0.3% to about 8% by weight
, or from about 0.3% to about 7%, or from about 0.3% to about 6%, or from about 0.3% to about 5%, or from about 0.5% to about 9% % by weight, or from about 0.5% to about 8% by weight
, or from about 0.5% to about 7%, or from about 0.5% to about 6%, or from about 0.5% to about 5%, or from about 1% to about 10% by weight , or from about 2 weight percent to about 10 weight percent, or from about 3 weight percent to about 10 weight percent, or from about 4 weight percent to about 10 weight percent.

With respect to the polyol premix composition, the polyester polyol can be present in the polyol premix in an amount of about 50% to about 98% by weight, based on the total weight of the components in the polyol premix composition. The blowing agent can be present in an amount from about 0.25% to about 50% by weight.

With respect to the polyol premix composition, the polyester polyol is from about 55% by weight of the polyol premix composition, based on the total weight of the components in the premix composition.
about 98% by weight, or about 60% to about 98% by weight, or about 65% to about 98% by weight, or about 70% to about 98% by weight, or about 75% to about 98% by weight, or About 80% by weight or more
about 98% by weight, or about 85% to about 98% by weight, or about 90% to about 98% by weight, or about 50% to about 95% by weight, or about 50% to about 90% by weight, or About 50% by weight or more
about 85% by weight, or about 60% to about 95% by weight, or about 60% to about 90% by weight, or about 60% to about 85% by weight, or about 60% to about 80% by weight, or About 65% by weight or more
present in the polyol premix composition in an amount of about 95% by weight, or from about 65% to about 90%, or from about 65% to about 85%, or from about 65% to about 80% by weight; can be done.

The blowing agent is from about 0.25 wt% to about 45 wt%, or from about 0.25 wt% to about 40 wt%, or from about 0.25 wt%, based on the total weight of the components of the polyol premix composition. to about 35% by weight, or from about 0.25% to about 30%, from about 0.25% to about 25% by weight,
or about 0.25 wt% to about 20 wt%, or about 0.25 wt% to about 15 wt%, or about 0
. 25 wt% to about 10 wt%, or about 0.25 wt% to about 5 wt%, or about 0.25 wt% to about 2 wt%, or about 1 wt% to about 50 wt%, or about 1 wt% % to about 45%, or from about 1% to about 40%, or from about 1% to about 35%, or from about 1% to about 30%, from about 1% to about 25%, or from about 1% to about 20%, or from about 1% to about 15%, or from about 1% to about 10%, or from about 1% to about 5%, or from about 1% to about 2 wt%, or about 5 wt% to about 50 wt%, or about 5 wt% to about 45 wt%, or about 5 wt% to about 40 wt%, or about 5 wt% to about 35 wt%, or about 5% by weight to about 30%
% by weight, from about 5% to about 25%, or from about 5% to about 20%, or from about 5% to
about 15 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 40 wt%, or about 10 wt% to about 35 wt%, or about 10 wt% to about 30 wt%, about 10% by weight to about 25%
% by weight, or from about 10% to about 20%, or from about 10% to about 15%, or about 1
5 wt% to about 50 wt%, or about 15 wt% to about 45 wt%, or about 15 wt% to about 40 wt%
% by weight, or from about 15% to about 35%, or from about 15% to about 30%, or about 1
5 wt% to about 25 wt%, or about 15 wt% to about 20 wt%, or about 20 wt% to about 50 wt%
% by weight, or from about 20% to about 45%, or from about 20% to about 40%, or about 2
0 wt% to about 35 wt%, or about 20 wt% to about 30 wt%, or about 20 wt% to about 25 wt%
It can be present in weight percent amounts.

A polyol premix composition can include a catalyst and a surfactant.

The polyol premix composition can include one or more of flame retardants, dyes, fillers, pigments, dispersants, cell stabilizers, and nucleating agents.

A polyol premix composition may be formed by combining a polyester polyol, a halogenated olefin blowing agent, and a compatibilizer. The blowing agent, or the polyester polyol, or both are preferably substantially dissolved in the compatibilizer by forming a stable solution, dispersion, and/or emulsion of the compatibilizer, blowing agent, and/or polyol Evenly distributed.

Generally, it is contemplated that the order and method of addition of the components in the compatibilizer blend and in forming the polyol premix may vary widely within the scope of the present invention. A compatibilizer may be added to the blowing agent before it is added to the remaining components of the premix composition.
Alternatively, the compatibilizer can be added to the polyester polyol before it is added to the remaining components of the premix composition. Alternatively, the compatibilizer can be added to the mixture of blowing agent, polyester polyol, and any other components. Alternatively, all of the components can be added simultaneously.

A polyester polyol may comprise one or more polyester polyols. A wide variety of polyester polyols may be used. Suitable polyester polyols include aromatic polyester polyols, aromatic polyethylene terephthalate polyols, aromatic carboxylic acid anhydrides, linear poly(diethylene adipate) glycol-based polyester polyols, dipropylene glycol, and combinations thereof, It is not limited to these.

One or more additional polyols may be present in addition to the polyester polyol(s). The additional polyol can be any polyol that reacts in a known manner with isocyanates in preparing polyurethane or polyisocyanurate foams. Useful additional polyols include sucrose-containing polyols, phenol-formaldehyde-containing polyols, glucose-containing polyols, sorbitol-containing polyols, methylglucoside-containing polyols, toluenediamine-containing polyols, Mannich base polyols, glycerin-containing polyols, ethylene glycol-containing polyols, diethylene glycol-containing polyols. , a propylene glycol-containing polyol, a graft copolymer of a polyether polyol and a vinyl polymer, a copolymer of a polyether polyol and a polyurea, one or more of (a) condensed with one or more of (b):

((a) glycerin, ethylene glycol, diethylene glycol, trimethylolpropane, ethylenediamine, pentaerythritol, soybean oil, lecithin, tall oil, palm oil, castor oil,

(b) ethylene oxide, propylene oxide, butylene oxide, mixtures of ethylene oxide and propylene oxide), or combinations thereof.

When a mixture of polyester polyol(s) and one or more additional polyols is used, the polyester polyol (total amount of all polyester polyols) is generally equal to the total amount of polyols (polyol(s) and additional polyols ) of about 1
Present in an amount of from about 99% by weight, the additional polyol is generally present in an amount of from about 1% to about 99% by weight of the total amount of polyols. The polyester polyol comprises from about 5% to about 99%, or from about 10% to about 99%, or from about 1% to about 99%, by weight of the polyol premix composition.
5 wt% to about 99 wt%, or about 20 wt% to about 99 wt%, or about 25 wt% to about 99 wt%
% by weight, or from about 30% to about 99% by weight, or from about 35% to about 99% by weight, or about 4
0 wt% to about 99 wt%, or about 45 wt% to about 99 wt%, or about 50 wt% to about 99 wt%
% by weight, or from about 55% to about 99% by weight, or from about 60% to about 99% by weight, or about 6
5 wt% to about 99 wt%, or about 70 wt% to about 99 wt%, or about 75 wt% to about 99 wt%
% by weight, or from about 80% to about 99% by weight, or from about 85% to about 99% by weight, or about 9
0 wt% to about 99 wt%, or about 95 wt% to about 99 wt%, or about 5 wt% to about 95 wt%, or about 10 wt% to about 95 wt%, or about 15 wt% to about 95 wt% % by weight, or about 20
% to about 95% by weight, or from about 25% to about 95% by weight, or from about 30% to about 95% by weight, or from about 35% to about 95% by weight, or from about 40% to about 95% by weight %, or about 45
% to about 95% by weight, or from about 50% to about 95% by weight, or from about 55% to about 95% by weight, or from about 60% to about 95% by weight, or from about 65% to about 95% by weight %, or about 70
% to about 95%, or from about 75% to about 95%, or from about 80% to about 95%, or from about 85% to about 95%, or from about 90% to about 95% by weight %, or about 5% to about 90%, or about 10% to about 90%, or about 15% to about 90%, or about 20% to about 90%, or about 25% by weight % to about 90%, or about 30% to about 90%, or about 35% to about 90%, or about 40% to about 90%, or about 45% to about 90% , or about 50% to about 90%, or about 55% to about 90%, or about 60% to about 90%, or about 65% to about 90%, or about 70% to about 90% by weight, or from about 75% to about 90% by weight, or from about 80% to about 90% by weight, or from about 85% to about 90% by weight, or from about 5% to about 85% by weight
, or about 10% to about 85%, or about 15% to about 85%, or 20% by weight
to about 85% by weight, or from about 25% to about 85% by weight, or from about 30% to about 85% by weight;
or about 35 wt% to about 85 wt%, or about 40 wt% to about 85 wt%, or about 45 wt%
to about 85% by weight, or from about 50% to about 85% by weight, or from about 55% to about 85% by weight;
or about 60 wt% to about 85 wt%, or about 65 wt% to about 85 wt%, or about 70 wt%
to about 85% by weight, or from about 75% to about 85% by weight, or from about 80% to about 85% by weight;
or about 85% to about 85%, or about 90% to about 85%, or about 5% to
about 80% by weight, or about 10% to about 80% by weight, or about 15% to about 80% by weight, or about 20% to about 80% by weight, or about 25% to about 80% by weight, or About 30% by weight or more
about 80% by weight, or about 35% to about 80% by weight, or about 40% to about 80% by weight, or about 45% to about 80% by weight, or about 50% to about 80% by weight, or About 55% by weight or more
about 80% by weight, or about 60% to about 80%, or about 65% to about 80%, or about 70% to about 80%, or about 75% to about 80%, or about 5% to about 75%, or about 10% to about 75%, or about 15% to about 75%, or about 20% to about 75%, or about 25% to about 75% by weight, or about 30% to about 75%, or about 35% to about 75%, or about 40% to about 75%, or about 45% to about 75%, or about 50% to about 75%, or about 55% to about 75%, or about 60% to about 75%, or about 65% to about 75%, or about 70% to about 75% % by weight, or from about 5% to about 70%, or from about 10% to about 7%
0 wt%, or about 15 wt% to about 70 wt%, or about 20 wt% to about 70 wt%, or about 25 wt% to about 70 wt%, or about 30 wt% to about 70 wt%, or about 35% by weight to about 7
0 wt%, or about 40 wt% to about 70 wt%, or about 45 wt% to about 70 wt%, or about 50 wt% to about 70 wt%, or about 55 wt% to about 70 wt%, or about 60% by weight to about 7
0 wt%, or about 65 wt% to about 70 wt%, or about 5 wt% to about 65 wt%, or about 1
0 wt% to about 65 wt%, or about 15 wt% to about 65 wt%, or about 20 wt% to about 65 wt%
% by weight, or from about 25% to about 65%, or from about 30% to about 65%, or about 3
5 wt% to about 65 wt%, or about 40 wt% to about 65 wt%, or about 45 wt% to about 65 wt%
% by weight, or from about 50% to about 65%, or from about 55% to about 65%, or about 6
0 wt% to about 65 wt%, or 5 wt% to about 60 wt%, or about 10 wt% to about 60 wt%, or about 15 wt% to about 60 wt%, or about 20 wt% to about 60 wt% %, or about 25% to about 60%, or about 30% to about 60%, or about 35% to about 60%, or about 40% to about 60%, or about 45% by weight % to about 60% by weight, or about 50% to about 60% by weight, or about 55% to about 60% by weight, or about 5% to about 55% by weight
, or about 10% to about 55%, or about 15% to about 55%, or about 20% to about 55%, or about 25% to about 55%, or about 30% ~ about 55% by weight
, or from about 35% to about 55%, or from about 40% to about 55%, or from about 45% to about 55%, or from about 50% to 55%, or from about 5% to about 50 wt%, or about 10 wt% to about 50 wt%, or about 15 wt% to about 50 wt%, or about 20 wt% to
about 50% by weight, or about 25% to about 50%, or about 30% to about 50%, or about 35% to about 50%, or about 40% to about 50%, or About 45% by weight or more
It can be present in an amount of about 50% by weight. Polyester polyols comprise at least about 20%, more preferably at least about 50% by weight of the polyols in the blend. The remaining portion of the total polyol is additional polyol.

The amount and composition of polyols used will depend in part on the type of foam being made.
The flexible foam is, for example, from about 80% by weight by weight of the polyol premix composition.
It may contain about 95% by weight of total polyols (polyester polyols and additional polyols, if any). From about 65% to about 85% by weight of total polyol can be present in the blown foam, for example, by weight of the polyol premix composition. For appliance foams, for example, from about 65% to about 85% by weight of total polyol can be present by weight of the polyol premix composition. Polyurethane
For ne, PUR) panel foams, for example, from about 65% to about 80% by weight of total polyol can be present, by weight of the polyol premix composition. In a polyisocyanurate (PIR) panel foam, for example, from about 65% to about 85% by weight of the total polyol can be present by weight of the polyol premix composition. PIR panel foams can be, for example, substantially all polyester polyols.

The halogenated olefin blowing agent preferably comprises a C3 or C4 halogenated olefin, even more preferably cis-1,1,1,4,4,4-hexafluorobut-2-ene (cis-HFO- 1336mzzm(Z)).

Auxiliary blowing agents may be present. Suitable auxiliary blowing agents include other hydrohaloolefins, fluorocarbons, chlorocarbons, chlorofluorocarbons, hydrocarbons, ethers, esters,
Examples include, but are not limited to, aldehydes, ketones, acetals, organic acids, atmospheric gases, gas generating materials, or combinations thereof. By gas generating material we mean a material that generates a gas, eg _CO2 , through decomposition or chemical reaction. Examples of gas generating materials include, but are not limited to, water, formic acid, or azodicarbonamide. Water reacts with isocyanates to form carbon dioxide. Formic acid reacts with isocyanates to form carbon dioxide and carbon monoxide.

Other hydrohaloolefins preferably contain at least one haloalkene, such as a fluoroalkene or chloroalkene containing 3 to 4 carbon atoms and at least one carbon-carbon double bond. Suitable hydrohaloolefins non-exclusively include trifluoropropene; tetrafluoropropene such as trans-HFO-1234ze or cis-H
FO-1234ze; pentafluoropropene, such as HFO-1225; hexafluorobutene, such as trans-HFO-1336mzz, or chlorotrifluoropropene, such as trans-HFO-1233zd, cis-HFO-1233zd, HFO-12
33xf; chlorodifluoropropene; chlorotetrafluoropropene, and combinations thereof. Tetrafluoropropene, pentafluoropropene, and chlorotrifluoropropene compounds having up to one F or Cl substituent on the unsaturated terminal carbon are preferred. trans-1,3,3,3-tetrafluoropropene (HFO-1234ze
); 2,3,3,3-tetrafluoropropene (HFO-1234yf); 1,1,3,
3-tetrafluoropropene; cis-1,2,3,3,3-pentafluoropropene (H
FO-1225ye); trans-1,2,3,3,3-pentafluoropropene (HF
O-1225ye); 1,1,1-trifluoropropene; 1,1,1,3,3-pentafluoropropene (HFO-1225zc); 1,1,1,3,3,3-hexafluorobuta- 2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc
); cis-1,1,1,2,3-pentafluoropropene (HFO-1225ye); trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd);
-chloro-3,3,3-trifluoropropene (HFO-1233xf); trans-1
, 1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz), or combinations thereof, and any and all structural, geometric, or stereoisomers of each of these. .

Preferred hydrohaloolefins have a Global Warming Potential of 150 or less, more preferably 100 or less, even more preferably 75 or less.
al, GWP). As used herein, "GWP" refers to "The Scientific Assessment of Oz
One Depletion, 2002, a report of the World
Meteorological Association's Global Ozo
Measured relative to the GWP of carbon dioxide and over a 100-year planning horizon, as defined in the New Research and Monitoring Project. Preferred hydrohaloolefins also preferably have an ozone depletion potential (Ozone De
pletion potential, ODP). As used herein,
"ODP" is defined in "The Scientific A
Assessment of Ozone Depletion, 2002, A repo
RT of the World Meteorological Association
on's Global Ozone Research and Monitoring
g Project”.

Other suitable blowing agents include HCFC-141b (CH3CCl2F), HCFC-1
42b (CH3CClF2), HCFC-22 (CHClF2), HFC-245fa (
CHF2CH2CF3), HFC-365mfc (CH3CF2CH2CF3), HFC
-227ea (CF3CHFCF3), HFC-134a (CH2FCF3), HFC-
152a (CH3CHF2), trans-1,2-dichloroethylene, propane, butane, isobutane, n-pentane, isopentane, cyclopentane, dimethyl ether,
methyl formate, methyl acetate, acetone, methylal, ethylal, carbon dioxide, water, formic acid,
Acetic acid, and mixtures or two or more thereof.

Blowing agents according to the present invention may be present over a range of concentrations based on foam type and/or application, and all such concentrations are within the scope of the present invention. The blowing agent is, for example, from about 0.25% to about 50%, or from 0.5% to about 50%, by weight of the polyol premix composition.
% by weight, or from about 1% to about 50%, or from about 2% to about 50%, or about 0.5%
% to about 40% by weight, or from about 1% to about 40% by weight, or from about 2% to about 40% by weight
, or about 0.5% to about 30%, or about 1% to about 30%, or about 2% by weight
to about 30% by weight, or from about 0.5% to about 25% by weight, or from about 1% to about 25% by weight;
or from about 2% to about 25%, or from about 0.5% to about 20%, or from about 1% to
about 20 wt%, or about 2 wt% to about 20 wt%, or about 0.5 wt% to about 15 wt%, or about 1 wt% to about 15 wt%, or about 2 wt% to about 15 wt% , or from about 0.5% to about 10%, or from about 1% to about 10%, or from about 2% to about 10% by weight, in the polyol premix composition.

Based on the teachings contained herein, one skilled in the art will be able to select the amount of blowing agent used for the type of foam being made. For example, flexible foams generally contain a relatively low concentration of blowing agent, preferably HFO-1336mzzm(Z), preferably about 0.2
5 wt% to about 10 wt%, or about 0.5 wt% to about 8 wt%, or about 0.5 wt% to about 6 wt%
%, or from about 0.5% to about 5%, or from 0.5% to about 4%. The blown foam preferably contains a blowing agent, preferably HFO-1336mzzm (Z
), preferably from about 4% to about 25%, or from about 4% to about 20%, or from about 4%
% to about 15% by weight, or from about 6% to about 12% by weight. foam for appliances,
PIR panel foams and PUR panel foams preferably contain a blowing agent, preferably HF
O-1336mzzm(Z), preferably in an amount of from about 5% to about 30%, or from about 10% to about 30%, or from about 15% to about 30% by weight.

HFO-13 when both HFO-1336mzzm(Z) and auxiliary blowing agent are present
36mzzm(Z) is preferably from about 1% to about 99% by weight of total blowing agent;
or from about 5% to about 99%, or from about 10% to about 99%, or from about 15% to
about 99% by weight, or about 20% to about 99% by weight, or about 25% to about 99% by weight, or about 30% to about 99% by weight, or about 35% to about 99% by weight, or About 40% by weight or more
about 99% by weight, or about 45% to about 99%, or about 50% to about 99%, or about 55% to about 99%, or 60% to about 99%, or about 65% to about 99%, or about 70% to about 99%, or about 75% to about 99%, or about 80% to about 99%, or about 85% to about 99% %, or about 90% to about 99% by weight, and the auxiliary blowing agent is preferably about 99% to about 1%, or about 95% to about 1%, by weight of the total blowing agent. 1% by weight, or from about 90% to about 1%, or from about 85% to about 1%, or from about 80% to about 1%, or from about 75% to about 1%, or about 70% to about 1%, or about 65% to about 1%, or about 60% to about 1%, or about 55% to about 1%, or about 50% to about 1% % by weight, or about 45% to about 1%, or about 40% to about 1%, or about 35% to about 1%, or about 30% to about 1%, or about 25% % to about 1%, or from about 20% to about 1%, or from about 15% to about 1%, or from about 10% to about 1% by weight.

The overall composition of the blowing agent blend can vary widely within the broad scope of the invention,
Based on the teachings contained herein, one skilled in the art will be able to tailor the specific blowing agent components and amounts to their specific needs, and the type and desired foam to be made. Including those based on foam properties.

The polyol premix composition may contain a surfactant. Surfactants are used to form a foam from the mixture and to control the cell size of the foam to obtain the desired cellular structure of the foam. Preferably, foams with uniformly sized small bubbles or cells therein are desirable, as they have the most desirable physical properties such as compressive strength and thermal conductivity. Also, the foam should have stable cells that do not collapse prior to formation or during foaming.

Suitable surfactants include silicone surfactants and non-silicone surfactants. The surfactant component is preferably about 0.1 wt% to about 10 wt%, or about 0.2 wt% to about 5 wt%, or about 0.2 wt%, by weight of the polyol premix composition. % to about 3.0%, or from about 0.5% to about 3.0% by weight, in the polyol premix composition.

The polyol premix composition contains a catalyst. Suitable catalysts include amine catalysts and non-amine catalysts. the catalyst is preferably from about 0.2 wt% to about 8.0 wt%, or from about 0.4 wt% to about 7.0 wt%, by weight of the polyol premix composition;
Or present in the polyol premix composition in an amount of about 0.5% to about 6.0% by weight.

Conventional flame retardants are preferably no more than about 20% by weight of the polyol premix, or about 1% by weight of the polyol premix.
It may optionally be incorporated in an amount of 5 wt% or less, or about 10 wt% or less. Some embodiments, such as appliance foams, typically do not contain flame retardants. Optional flame retardants include:
Tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, tris(,3-dichloropropyl) phosphate, tri(2-chloroisopropyl) phosphate ), tricresyl phosphate, tri(2,2-dichloroisopropyl) phosphate, diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonate, dimethylmethylphosphonate, tri(2,3-dibromopropyl) phosphate, Tri(1,3-dichloropropyl) phosphate and tetra-cis-(2-chloroethyl) ethylene diphosphate, triethyl phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate materials, polyvinyl chloride, melamine, and the like, but are not limited to these.

In addition to the ingredients already mentioned, dyes, fillers, pigments, dispersants, cell stabilizers, nucleating agents (
Other ingredients such as 3M's perfluorinated compounds, PF-5056 and FA-188)
It can be included in the preparation of foams. Other ingredients are typically included in amounts up to a total of 20%, or 15% or less, or 10% or less, or 5% or less, by weight of the polyol premix composition. Conventional fillers for use herein include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fiber, carbon black, and silica. Pigments that may be used herein include any conventional pigment such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chrome green, chrome yellow, iron blue sienna, molybdenum orange, as well as organic pigments such as para red. , benzidine yellow, toluidine red, toner, and phthalocyanine.

The polyol premix composition may contain from about 50% to about 98% by weight polyester polyol and any additional polyol. If any additional polyols are present, from about 10% to about 99% by weight (based on total weight of polyol component) of polyester polyol, and from about 1% to about 90% by weight (based on total weight of polyol component) based on) may be present, such as polyether polyols and Mannich polyols. The polyol premix composition may contain from about 0.25% to about 50% by weight blowing agent (based on total polyol premix). The blowing agent is HFO-1336mzzm (
Z), or a mixture of HFO-1336mzzm(Z) and an auxiliary blowing agent. HFOs
-1336mzzm(Z) can be present in an amount from about 40% to about 99% by weight of the blowing agent component;
It can be present in an amount of 60% by weight. The compatibilizer may be an alcohol and has a content of about 0
. 01% to about 10% by weight. From about 0.2 to about 5% by weight surfactant may be present. The polyol premix composition can contain from about 0.1 wt% to about 8.0 wt% catalyst. The polyol premix may contain up to about 20% by weight flame retardant and up to about 20% by weight other additives.

Preferred formulations of foams used in appliances, PIR panels, and PUR panels are:
Based on the total polyol premix composition, from about 65% to about 85% by weight polyester polyol and optional additional polyols (from about 20% to about 99% by weight polyester polyol and from about 1% to about 80% by weight of additional polyols (if any) (based on total weight of polyols)). The polyol premix composition contains from about 15 wt% to about 3
0 wt% blowing agent (based on total polyol premix) (cis-HFO-1336mz
zm (Z), or from about 92% to about 97% by weight of cis-HFO-1336mzzm (Z)
and about 3% to about 8% by weight water). The compatibilizer can be an alcohol and can be present in an amount from about 0.01% to about 10% by weight. about 0.2
From to about 5% by weight of surfactant, and from about 0.1% to about 6% by weight of catalyst may be present. The polyol premix composition may optionally contain about 15% by weight flame retardant and about 10% by weight other additives.

A preferred formulation for blown foam applications comprises from about 65% to about 85% by weight polyester polyol and optional additional polyol (from about 40% to about 99% by weight, based on the total polyol premix composition). polyester polyol and from about 1% to about 60% by weight of additional polyol (if any) (based on total weight of polyols). The polyol premix composition preferably comprises from about 6% to about 12% by weight blowing agent (based on total polyol premix composition) (cis-HFO-13
36mzzm (Z), or from about 60% to about 85% by weight of cis-HFO-1336mzz
m(Z) and about 15% to about 40% by weight water). The compatibilizer can be an alcohol and can be present in an amount from about 0.01% to about 10% by weight. From about 0.2% to about 5% by weight of surfactant, from about 0.1% to about 8% by weight of catalyst may be present. The polyol premix composition may contain 15% by weight flame retardant and 10% by weight other additives.

A preferred flexible foam formulation comprises from about 80% to about 95% by weight polyester polyol and optionally an additional polyol (from about 10% to about 99% by weight polyester polyol), based on the total polyol premix composition. and from about 1% to about 90% by weight of additional polyol (if present) (based on total weight of polyols). The polyol premix composition contains from about 0.5% to about 4% by weight of a blowing agent (based on the total polyol premix composition) (cis-HFO-1336mzzm(Z), or from about 40% to about 50% by weight. %
of cis-HFO-1336mzzm (Z) and about 50% to about 60% by weight of water). The compatibilizing agent may be an alcohol and ranges from about 0.01% by weight to about 10% by weight.
It can be present in weight percent amounts. about 0.2 to about 5% by weight surfactant, and about 0.1
% to about 3.5% by weight of catalyst may be present. The polyol premix composition contains about 10
It may contain weight percent flame retardants and about 10 weight percent other additives.

Preferred distribution enhancing components for aromatic polyester polyols and cis-HFO-1336mzzm(Z) include alcohols, alkylphenol ethoxylates, ethers, chlorinated solvents.

One preferred polyol premix has 1 to 10 carbon atoms, more preferably 1
5 carbon atoms, more preferably 2-5 carbon atoms, more preferably 2-4 carbon atoms, and even more preferably ethanol.

One preferred polyol premix is an aromatic polyester polyol and a cis-
HFO-1336mzzm (Z) and nonylphenol ethoxylate (ethyoxy
late).

One preferred polyol premix is an aromatic polyester polyol and a cis-
Contains HFO-1336mzzm(Z) and ethylene glycol mono-butyl ether.

One preferred polyol premix is an aromatic polyester polyol and a cis-
Contains HFO-1336mzzm(Z) and 2-chloropropane.

Aromatic carboxylic anhydride (phthalic acid) polyester polyol and cis-HFO-13
Preferred distribution-enhancing components for 36mzzm(Z) include alcohols, alkylphenol ethoxylates, glycols, ethers and acetals, benzene, ketones,
Chlorinated solvents, carbonates, and solvents are included.

One preferred polyol premix is an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z) and 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. , more preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably ethanol.

One preferred polyol premix comprises aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and nonylphenol ethoxylate.

One preferred polyol premix comprises an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and dipropylene glycol.

One preferred polyol premix comprises aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and dipropylene glycol methyl ether.

One preferred polyol premix comprises an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and methylal.

One preferred polyol premix comprises aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and ethylene glycol mono-butyl ether.

One preferred polyol premix comprises an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and 1,3-diisopropenylbenzene.

One preferred polyol premix comprises an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and isopropenylbenzene.

One preferred polyol premix comprises aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and acetone.

One preferred polyol premix comprises aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and methyl ethyl ketone.

One preferred polyol premix comprises an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and methyl formate.

One preferred polyol premix is aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), trans-1,2-
including dichloroethylene.

One preferred polyol premix comprises an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and 2-chloropropane.

One preferred polyol premix comprises an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and propylene carbonate.

One preferred polyol premix comprises an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and dioctyl phthalate.

One preferred polyol premix comprises an aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and toluene.

One preferred polyol premix is aromatic carboxylic anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), 1-propoxy-2
- propanol.

Preferred distribution-enhancing components for aromatic polyester polyol diols and cis-HFO-1336mzzm(Z) include alcohols, glycols, and ethers.

One preferred polyol premix is an aromatic polyester polyol diol, cis-HFO-1336mzzm(Z) and 1 to 10 carbon atoms, more preferably 1
and monofunctional acyclic alcohols having up to 5 carbon atoms, more preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably ethanol.

One preferred polyol premix includes an aromatic polyester polyol diol, cis-HFO-1336mzzm(Z), and ethylene glycol.

One preferred polyol premix comprises an aromatic polyester polyol diol, cis-HFO-1336mzzm(Z), and ethylene glycol mono-butyl ether.

Aliphatic adipate diethylene glycol-based polyester polyol and cis-HFO-
Preferred distribution-enhancing components for 1336mzzm(Z) include alcohols, alkylphenol ethoxylates, ethers and acetals, chlorinated solvents, and ketones.

One preferred polyol premix is a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z) and 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms,
monofunctional acyclic alcohols, more preferably having 2 to 4 carbon atoms, and even more preferably ethanol.

One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and nonylphenol ethoxylate.

One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and dipropylene glycol methyl ether.

One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and methylal.

One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and ethylene glycol mono-butyl ether.

One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and isopropenylbenzene.

One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and acetone.

One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and methyl ethyl ketone.

One preferred polyol premix is a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), trans-
1-chloro-3,3,3-trifluoropropene.

One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and methyl formate.

Preparation of polyurethane or polyisocyanurate foams using the compositions described herein may follow any of the methods well known in the art and can be found at Saun
ders and Frisch, Volumes I and II Polyure
Thanes Chemistry and Technology, 1962, John
n Wiley and Sons, New York, N.W. Y. or Gum, Rees
e, Ulrich, Reaction Polymers, 1992, Oxford U.
diversity Press, New York, N.W. Y. or Klempner
and Sendijarevic, Polymeric Foams and Foam
m Technology, 2004, Hanser Gardner Publica
tions, Cincinnati, Ohio. Generally, polyurethane or polyisocyanurate foams are prepared by combining other ingredients such as isocyanates, polyol premix compositions, and optional flame retardants, colorants, or other additives. These foams can be rigid, flexible, or semi-rigid and can have a closed cell structure, an open cell structure, or a mixture of open and closed cells.

Providing the components for polyurethane or polyisocyanurate foams in a pre-blended formulation is convenient in many applications. Most typically, the foam formulation is pre-blended into two components. Isocyanates and optionally other isocyanate compatible ingredients comprise a first component, commonly referred to as the "A" component. Polyol mixture compositions containing surfactants, catalysts, blowing agents, and any other ingredients include a second component, commonly referred to as the "B" component. In any given application, the "B" component may not contain all of the components listed above. For example, some formulations omit flame retardants when flame retardancy is not a desired foam property. therefore,
Polyurethane or polyisocyanurate foams are readily prepared by bringing together the sub-components of A and B, either by hand mixing for small scale preparations, and preferably by mechanical mixing techniques, Form blocks, slabs, laminates, cast-in-place panels, and other articles such as blown foam, floss, and the like. optionally flame retardants, colorants, auxiliary blowing agents,
Other ingredients, such as water and even other polyols, can be added as a stream to the mixing head or reaction site. Most conveniently they are all incorporated into one B component as described above.

A foamable composition suitable for forming polyurethane or polyisocyanurate foams may be formed by reacting an organic polyisocyanate and the polyol premix composition described above. Any organic polyisocyanate can be used in polyurethane or polyisocyanurate foam synthesis, including aliphatic and aromatic polyisocyanates. Suitable organic polyisocyanates include aliphatic,
Cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates are included. These are described, for example, in U.S. Pat. Nos. 4,868,224, 3,401,190, 3,454,
606, 3,277,138, 3,492,330, 3,001,9
73, 3,394,164, 3,124,605, and 3,201,
372. Aromatic polyisocyanates are preferred as a class.

A representative organic polyisocyanate has the formula:
R(NCO)z
where R is an aliphatic group, an aromatic group, or a mixture thereof, and z is an integer corresponding to the valence of R and is at least two. Representative organic polyisocyanates contemplated herein include, for example, aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanates , crude toluene diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate; aromatic triisocyanates such as 4,4′,4″-triphenylmethane triisocyanate, 2,4,6-toluene diisocyanate; aromatic tetraisocyanates, 4,4′-dimethyldiphenylmethane-2,2′5,5-′tetraisocyanate, etc.; arylalkyl polyisocyanates such as xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene-1,6-diisocyanate, lysine diisocyanate methyl and mixtures thereof. Other organic polyisocyanates include polymethylene polyphenyl isocyanate, hydrogenated methylene diphenyl isocyanate, m-phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2
,4-diisocyanate, 4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, and 3,3′-dimethyl Diphenylmethane-4,4'-diisocyanate may be mentioned. Typical aliphatic polyisocyanates are alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorene diisocyanate, 4
, 4′-methylenebis(cyclohexyl isocyanate). Typical aromatic polyisocyanates include m- and p-phenylene diisocyanates, polymethylene polyphenyl polyisocyanates, 2,4- and 2,6-toluene diisocyanates, dianisidine diisocyanates, bitolein isocyanates, 1,4- diisocyanate, bis(
4-isocyanatophenyl)methene, bis(2-methyl-4-isocyanatophenyl)methane, and the like. A preferred polyisocyanate is polymethylene polyphenyl polyisocyanate, especially from about 30 to about 85 weight percent methylene bis(phenyl isocyanate).
and the remainder of the mixture is polymethylene polyphenyl polyisocyanate of functionality higher than 2. In certain cases, so-called isocyanate prepolymers can also be used. A prepolymer is formed by combining an excess of diisocyanate with a polyol (polyester polyol or polyether polyol). These polyisocyanates are prepared by conventional methods known in the art. In the present invention, polyisocyanates and polyols are used in amounts that provide NCO/OH stoichiometric ratios in the range of about 0.9 to about 5.0. In the present invention, the NCO/OH equivalent ratio is preferably from about 0.9 to about 4, or from about 0.95 to about 3. Suitable organic polyisocyanates include polymethylene polyphenyl polyisocyanate, methylene bis(phenyl isocyanate), toluene diisocyanate, or combinations thereof.

In preparing the polyisocyanurate foam, a trimerization catalyst is preferably used to convert the blend, in conjunction with excess A component, into a polyisocyanurate-polyurethane foam. The trimerization catalysts used include, but are not limited to, glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylates, and alkali metal carboxylates, and mixtures of various types of catalysts. It can be any catalyst known to those skilled in the art.
Preferred species within this class are potassium acetate, potassium octanoate, and N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

Polyurethane or polyisocyanurate foams produced have densities from 0.5 lbs/ft 3 to about 60 lbs/ft 3 , or from about 0.5 to about 20.0 lbs/ft 3 , or from about 0.5 to about 60 lbs/ft 3 . It can vary from about 15 pounds per cubic foot. The density obtained depends on how much blowing agent or mixture of blowing agents, plus the amount of auxiliary blowing agents such as water or co-blowing agents, are present in the A and/or B components, or the foam is prepared. It is a function of what is added when. These foams can be rigid, flexible, or semi-rigid foams and can have a closed cell structure, an open cell structure, or a mixture of open and closed cells. These foams are used in a variety of well-known applications including, but not limited to, thermal insulation, cushioning, flotation, packaging, adhesives, void filling, crafting and decoration, and shock absorption.

The following non-limiting examples serve to illustrate the invention.

Comparative Example 1 Distribution of Blowing Agents in Polyols Testing the ability of certain polyols to form stable and uniform distributions of HFO-1336mzzm(Z) in the absence of the compatibilizer aspect of the present invention. did. Each polyol identified in Table 1 was tested by placing a predetermined amount of polyol in a 3 oz. glass pressure vessel and recording the height and weight of the polyol. For each test, then HFO-13
Each of the liquid blowing agents identified in Table 1 containing 36 mzzm(Z) was added to the vessel for a total weight of 70 grams of polyol and blowing agent in the vessel to produce 5 weight percent blowing agent and 95 weight percent polyol. was added in an amount The tube assembly was sealed and the height and weight of the polyol and blowing agent components were recorded together. The components were then mixed thoroughly to obtain a homogeneous distribution of the blowing agent in the polyol. Visual observations of liquid height and condition of the mixture of components were recorded versus test temperature. If a homogenous mixture was produced, i.e., if a concentration of 5% by weight of the blowing agent was evenly distributed by visual observation in the polyol, this result is referred to as 5% by weight and is referred to as "wt% homogenous distribution". Recorded in the column of Table 2 entitled For any test, if the sample did not show the presence of a visually homogeneous mixture, i.e., if phase separation was observed, the height of each layer was recorded and this height and the polyol and blowing agent Based on known density information, the amount of blowing agent uniformly distributed in the polyol in weight percent was reported. The test was performed at room temperature (RT), 32°C (90°F), and 54°C (13
0° F.).

Table 1 shows blowing agents, blowing agent concentrations, and polyols tested.

As can be seen from Table 2 above, Polyol D (1,4-butanediol chain extender diol) was HFO-1336mz
It was not possible to form a homogeneous mixture with zm(Z). The maximum amount of HFO-1336mzzm(Z) that could be uniformly distributed in Polyol D even at a high temperature of 54° C. was
Only 2%. In contrast, other polyols were able to form uniform distributions of about 5 wt% HFO-1336mzzm(Z) even in the absence of compatibilizers. generally,
The ability to achieve uniform distribution of all blowing agents tested improved at higher temperatures.

The test was repeated with other polyols. Each liquid blowing agent identified in Table 3, including HFO-1336mzzm(Z), was added to 21% by weight blowing agent and 79% by weight polyol in the container with a total weight of polyol and blowing agent in the container of 70 grams. Each polyol identified in Table 3 was tested by adding an amount that produced a If a homogenous mixture was produced, i.e., if the 21 wt% concentration of blowing agent was uniformly distributed in the polyol by visual observation, this result was labeled as 21 wt% and "wt% homogenous distribution". Recorded in the column of Table 4 entitled
For any test, if the sample did not show the presence of a visually homogeneous mixture, i.e., if phase separation was observed, the height of each layer was recorded and this height and the polyol and blowing agent Based on known density information, the amount of blowing agent uniformly distributed in the polyol in weight percent was reported. The test was performed at room temperature (RT), 32°C (90°F), and 54°C (130°F).
).

Table 4 below shows the blowing agents, blowing agent concentrations, and polyols tested.

In the absence of the present invention, HFO-1336mzzm(Z) is HF
It had a uniform distribution in polyols FI at significantly lower levels than O-1233zd(E). HFO-1233zd (E) is HFO-1336mzzm (Z) and HFC-2
It had excellent uniformity of distribution in polyols F to I compared to 45fa.

In the absence of the present invention, HFO-1336mzzm(Z) is HF
It had a uniform distribution in polyol O at significantly lower levels than O-1233zd(E). HFO-1233zd (E) is HFO-1336mzzm (Z) and HFC-245
It had excellent uniformity of distribution in polyols K-O compared to fa.

From this test, HFO-1336mzzm(Z) had a uniform distribution with significantly lower levels of certain polyester polyols, but polyester polyols did not appear to have similar problems.

Example 1: Compatibilizer for use with HFO-1336mzzm(Z) Different classes of polyester polyols, specifically aromatic carboxylic anhydride (phthalic acid) polyester polyols (Polyol F), aromatic polyester polyols ( Polyol O), aromatic polyester polyol diol (Polyol P), and linear aliphatic diethylene glycol adipate-based polyester polyol (Polyol Q), the ability of HFO-1336mzzm(Z) to be uniformly distributed in certain compatibilizing A study was undertaken to determine the extent to which the agent was able to enhance.

A first set of tests was conducted to demonstrate the ability of various distributing agents to uniformly distribute in the tested polyols. 17 grams of each polyol tested was transferred to a small vial and the polyol height was recorded. An appropriate weight of 8 grams of the identified compatibilizer was added to the polyol and reported whether a uniform distribution formed upon mixing.

A second set of tests was performed to demonstrate the ability of various distributing agents to distribute uniformly in the blowing agent HFO-1336mzzm(Z). Transfer 8.5 grams of blowing agent to a small vial and record the height of the blowing agent. 1.5 grams of the identified compatibilizer was added to the blowing agent and reported whether a uniform distribution formed upon mixing.

A third set of tests was conducted to demonstrate the ability of various distributing agents to uniformly distribute with the blowing agent HFO-1336mzzm(Z) and the polyols tested. The mixtures shown in the first test and the second test were repeated as indicated above, then 16 grams of the first mixture (polyol/compatibilizer mixture) and 4 grams of the second mixture (HFO- 13
36mzzm(Z)/compatibilizer mixture) to mix the polyol, HFO-1336mz
A mixture of zm (Z) and the indicated compatibilizer (UDA) was formed. Formation of a uniform distribution of blowing agent and polyol and compatibilizer was reported by visual observation during mixing. For convenience, the uniform distribution agent is referred to as UDA (uniform distribution agent) in Tables 5A-5F.
n agent).

As shown in Tables 5A-F above and Example 1, lower molecular weight alcohols are excellent compatibilizers for HFO-1336mzzm(Z) in all polyester polyols tested. HF in polyester polyols for glycols and ethers
The only glycol or ether that is a universal compatibilizer for O-1336mzzm(Z) is ethylene glycol mono-butyl ether. Ethylene glycol, diisopropylene glycol, dipropylene glycol methyl ether, and methylal can be used as compatibilizers for some types of polyester polyols. Neither benzene nor ketones were universal compatibilizers for HFO-1336mzzm(Z). However, this class of materials has been found to be effective compatibilizers for HFO-1336mzzm(Z) in polyester polyols with lower functionality (eg, Polyols F and Q). Oils and hydrocarbons are H in polyester polyols.
It did not provide the compatibilizer's ability to improve the miscibility of FO-1336mzzm(Z). Most co-blowing agents do not act as compatibilizers at the levels tested.
However, HFO-1233zd(E) is a compatibilizer for Polyol Q,
Methyl formate is a polyester polyol with lower functionality (e.g., Polyol F
and Q). Many commonly used raw materials do not function as universal compatibilizers for HFO-1336mzzm(Z) in polyester polyols. However, some are effective against polyester polyols with lower functionality. For example, trans-1,2-dichloroethylene, 2-chloropropane, propylene carbonate, and toluene are effective against both polyols F and Q, while tris(1-chloro-2-propyl) phosphate Polyol Q was effective and 1-propoxy-2-propanol was effective for Polyol F.

As can be seen from Tables 5A-5F above, compatibilizers and mixtures thereof according to the present invention form a uniform distribution with compatibilizers of polyols F and O and HFO-1233zd(E), while and, as reported in Comparative Example 1, a uniform distribution was not formed otherwise.

Example 2 - Minimum Concentration Range Twenty-seven grams of the polyol to be evaluated was added to a large vial and the height of the polyol within the vial was measured. Eight grams of HFO-1336mzzm was added to the vial and the liquid height was measured. The vial was sealed and mixed well. The height of the separation layer was measured (it is
HFO-1336mzzm, which was not evenly distributed in solution). 0.2 grams of compatibilizer was added to the vial. The vial was sealed and the solution mixed well. The layer height in the vial was recorded. Additional compatibilizer was added to the solution until a homogeneous solution was obtained. The amount was then recorded. Table 6 shows the results.

Example 3A: Stability Study: Ternary Mixture at 4-6 Months HFO-1336mzzm(Z) + Polyol + UD Reported in Tables 5A-5F Above
Mixtures of A were stored in sealed containers under ambient (room temperature) conditions for a period of 4-6 months to assess long-term stability. Formation of a uniform distribution of blowing agent and polyol and compatibilizer was reported by visual observation during initial mixing and during storage for a period of 4-6 months. Tables 7A-C show the results.

Example 3B: Stability study: 1 year HFO-1336mzzm(Z) + polyol + UD reported in Tables 7A-7C above
A ternary mixture was stored in a sealed container under ambient (room temperature) conditions for a period of one year to assess long-term stability. The formation of a uniform distribution of blowing agent and polyol and compatibilizer is reported by visual observation upon initial mixing and upon storage for a period of one year. Mixtures showing stability at 4-6 months are observed to be stable at 1 year.

Example 3C: Stability Studies: Binary Mixtures at 4-6 Months and 1 Year The HFO-1336mzzm(Z)+UDA and polyol+UDA binary mixtures reported in Tables 5A-5F above were tested at 4-6 months and 1 year. Long term stability is assessed by storing in a sealed container under ambient (room temperature) conditions for a period of 1 year. The presence or absence of formation of a uniform distribution of blowing agent and compatibilizer and polyol and compatibilizer is reported by visual observation upon storage for periods of 4-6 months and 1 year. The binary mixture is observed to be stable at 4-6 months and 1 year.

Example 4: Compatibilizer for use with HFO-1336mzzm(Z) in 1,4-butanediol Specifically in butanediol, more specifically in alkanediols with 1,4-butanediol Studies are undertaken to determine the extent to which a particular compatibilizer can enhance the ability of HFO-1336mzzm(Z) to distribute uniformly.

A first set of tests is conducted to demonstrate the ability of various distributing agents to distribute uniformly in 1,4-butanediol. Transfer 17 grams of 1,4-butanediol to be tested to a small vial and record the height of the material. Add 8 grams of the identified compatibilizer to the material and see if a uniform distribution forms upon mixing and then upon storage in a sealed container under ambient (room temperature) conditions over a 6 month and 1 year storage period. report.

A second set of tests is conducted to demonstrate the ability of various distributing agents to distribute uniformly in the blowing agent HFO-1336mzzm(Z). Transfer 8.5 grams of blowing agent to a small vial and record the height of the blowing agent. 1.5 grams of the identified compatibilizer was added to the blowing agent and a uniform distribution was formed upon mixing and then upon storage in a sealed container under ambient (room temperature) conditions over 6 months and 1 year storage periods. report whether

A third set of tests is performed to demonstrate the ability of various distributing agents to uniformly distribute together with the blowing agents HFO-1336mzzm(Z) and 1,4-butanediol. The mixtures shown in the first test and the second test were repeated as indicated above, then 16 grams of the first mixture (polyol/compatibilizer mixture) and 4 grams of the second mixture (HFO-
1336mzzm(Z)/compatibilizer mixture) to form materials, HFO-1336mzz
m(Z), and the indicated compatibilizer mixture, which is identified in Table 8 below as "1336
+ Polyol + UDA”. The presence or absence of formation of a uniform distribution of blowing agent and material and compatibilizer is reported in Table 8 below by visual observation upon initial mixing and upon storage for periods of 6 months and 1 year. For convenience, uniform distribution agents are identified as UDA in the tables.

As can be seen from Table 8 above, all compatibilizers and mixtures thereof according to the present invention form a uniform distribution of 1,4-butanediol and HFO-1336mzzm(Z) with the compatibilizer. while a uniform distribution, as reported in Comparative Example 1, was not otherwise formed.

Example 5: Compatibilizer for use with HFO-1336mzzm(Z) in other polyols Polyol A, Polyol B, Polyol C, Polyol E, Polyol G, Polyol H, Polyol I, Polyol K, Polyol L, Repeat the test reported in Example 4 above for the polyols except for each of the polyols identified as Polyol M, Polyol N, aromatic polyethylene terephthalate polyol, and dipropylene glycol polyol. Acceptable results are obtained both upon initial mixing and after the storage period shown in Example 2.

Polyols A-E can be used in a variety of foam applications including, but not limited to, integral skin foams. Polyols FI can be used in a variety of foam applications including, but not limited to, boardstock foams. Polyol K~
O can be used in a variety of foam applications including, but not limited to, blown foam. Polyol P can be used in a variety of foam applications including, but not limited to, boardstock foam. Polyol Q can be used in a variety of foam applications including, but not limited to, flexible foams.

Example 6: Compatibilizer for use with HFO-1233zd(E) in polyols Each of the polyols identified as Polyols A-Q and HFO-1233zd(E)
The test reported in Example 4 above for polyols is repeated using polyester terephthalate polyols except Acceptable results are obtained both upon initial mixing and after the storage period shown in Example 2.

Although the invention has been particularly shown and described with reference to preferred embodiments, it will be readily apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. will be understood. It is intended that the claims be interpreted to cover the disclosed embodiment, those alternatives that have been mentioned above and all equivalents thereof.

Although the invention has been particularly shown and described with reference to preferred embodiments, it will be readily apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. will be understood. It is intended that the claims be interpreted to cover the disclosed embodiment, those alternatives that have been mentioned above and all equivalents thereof.
This specification includes the following aspects of the invention.
[1]
A polyol premix composition comprising:
a halogenated olefin blowing agent;
a polyester polyol;
and a distribution-enhancing component comprising at least one organic compound having 1 to 40 carbon atoms, which remains a substantially homogeneous mixture when stored under ambient conditions for a period of 4 months. wherein said at least one organic compound is present in said premix in an amount effective to enhance the ability of said halogenated blowing agent and said polyol to form a substantially homogeneous blend in .
[2]
The polyol premix composition of [1], wherein the distribution enhancing component has one or more hydroxyl groups and 1 to 25 carbon atoms.
[3]
The polyol premix composition of [2], wherein the distribution-enhancing components include alcohols, glycols, ethers, acetals, benzene, ketones, chlorinated solvents, carbonates, solvents, and surfactants.
[4]
The polyol premix composition according to [3], wherein the halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobut-2-ene.
[5]
The distribution enhancing component comprises acyclic alcohols having 1 to 10 carbon atoms, cyclic alcohols having 6 to 40 carbon atoms, alkylphenols and alkylphenol ethoxylates, dipropylene glycol, diisopropylene glycol, di Propylene glycol methyl ether, methylal, ethylene glycol mono-butyl ether, 1,3-diisopropylbenzene, isopropylbenzene, 1,3-diisopropenylbenzene, isopropenylbenzene, acetone, methyl ethyl ketone, 2-chloropropane, trans-1-chloro- one or more of 3,3,3-trifluoropropene, methyl formate, propylene carbonate, dioctyl phthalate, toluene;
The polyol premix composition according to [1], wherein the halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobut-2-ene.
[6]
said distribution enhancing component comprises one or more of ethanol, methanol, isopropanol, n-butanol, 2-propanol, 1-pentanol, 3-methyl-2-butanol, and 2-methyl-1-propanol; The polyol premix composition according to [5].
[7]
The polyol premix composition of [1], wherein the distribution enhancing component is present in an amount of 0.5% to 10% by weight based on the total weight of the blend.
[8]
A polyol premix composition comprising:
a polyester polyol;
a halogenated olefin blowing agent;
and a distribution-enhancing component comprising at least one organic compound having from 1 to 40 carbon atoms, and the ability of said halogenated olefin blowing agent and said polyester polyol to form stable and substantially homogeneous compositions. A polyol premix composition, wherein said distribution reinforcing component is present in said polyol premix composition in a reinforcing effective amount.
[9]
The polyol premix composition of [8], wherein the distribution enhancing component has one or more hydroxyl groups and 1 to 25 carbon atoms.
[10]
The polyol premix composition of [8], wherein the distribution-enhancing component comprises one or more of alcohols, glycols, ethers, acetals, benzene, ketones, chlorinated solvents, carbonates, solvents, and surfactants. thing.
[11]
The polyol premix composition of [8], wherein the halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobut-2-ene.
[12]
The distribution-enhancing component is present in an amount of at least 1.7% by weight of the polyol premix composition, ethanol, methanol, isopropanol, n-butanol, 2-propanol, 1-pentanol, 3-methyl-2- The polyol premix composition of [11], comprising one or more of butanol and 2-methyl-1-propanol.
[13]
The polyester polyol and any additional polyols are present in an amount from 50% to 98% by weight of the polyol premix composition, and the halogenated olefin blowing agent is present at 0.25% by weight of the polyol premix composition. % to 50% by weight, and wherein said distribution enhancing component is present in an amount of 0.01% to 10% by weight of said polyol premix composition. thing.
[14]
The polyester polyol and any additional polyols are present in an amount from 80% to 95% by weight of the polyol premix composition, and the halogenated olefin blowing agent is present at 0.25% by weight of the polyol premix composition. % to 10% by weight, and wherein the distribution enhancing component is present in an amount of 0.01% to 10% by weight of the polyol premix composition. thing.
[15]
The polyol premix composition of [8], wherein said stable, substantially homogeneous composition remains a substantially homogeneous mixture when stored under ambient conditions for a period of 4 months.
[16]
A method of forming a polyol premix composition comprising:
Combining a polyester polyol, a halogenated olefin blowing agent, and a distribution enhancing component comprising at least one organic compound having from 1 to 40 carbon atoms to form a stable, substantially uniform composition wherein said distribution enhancing component is present in said polyol premix composition in an amount sufficient to enhance the performance of said halogenated olefin blowing agent and said polyester polyol.
[17]
The distribution-enhancing components include alcohols, glycols, ethers, acetals, benzene, ketones, chlorinated solvents, carbonates, solvents, and surfactants, and the halogenated olefin blowing agents include cis-1,1,1, The method of [16], including 4,4,4-hexafluorobut-2-ene.
[18]
The method of [16], wherein said stable, substantially homogeneous composition remains a substantially homogeneous mixture when stored under ambient conditions for a period of 4 months.
[19]
A foamable composition comprising a mixture of an organic polyisocyanate and the polyol premix composition described in [8].
[20]
The foamable composition of [19], wherein the organic polyisocyanate comprises polymethylene polyphenyl isocyanate, methylene bis(phenyl isocyanate), toluene diisocyanate, or combinations thereof.

Claims (20)

A polyol premix composition comprising:
a halogenated olefin blowing agent;
a polyester polyol;
and a distribution-enhancing component comprising at least one organic compound having 1 to 40 carbon atoms, which remains a substantially homogeneous mixture when stored under ambient conditions for a period of 4 months. wherein said at least one organic compound is present in said premix in an amount effective to enhance the ability of said halogenated blowing agent and said polyol to form a substantially homogeneous blend in . The polyol premix composition of claim 1, wherein the distribution enhancing component has one or more hydroxyl groups and 1 to 25 carbon atoms. 3. The polyol premix composition of claim 2, wherein said distribution-enhancing components include alcohols, glycols, ethers, acetals, benzenes, ketones, chlorinated solvents, carbonates, solvents, and surfactants. 4. The polyol premix composition of claim 3, wherein said halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobut-2-ene. the distribution-enhancing component is an acyclic alcohol having 1-10 carbon atoms, 6-40
cyclic alcohols having 1,3 carbon atoms, alkylphenols and alkylphenol ethoxylates, dipropylene glycol, diisopropylene glycol, dipropylene glycol methyl ether, methylal, ethylene glycol mono-butyl ether, 1,3
- diisopropylbenzene, isopropylbenzene, 1,3-diisopropenylbenzene, isopropenylbenzene, acetone, methyl ethyl ketone, 2-chloropropane, trans-1-chloro-3,3,3-trifluoropropene, methyl formate, propylene carbonate,
including one or more of dioctyl phthalate, toluene,
The polyol premix composition of claim 1, wherein said halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobut-2-ene. said distribution enhancing component comprises one or more of ethanol, methanol, isopropanol, n-butanol, 2-propanol, 1-pentanol, 3-methyl-2-butanol, and 2-methyl-1-propanol; 6. The polyol premix composition of claim 5. The polyol premix composition of claim 1, wherein said distribution enhancing component is present in an amount of 0.5% to 10% by weight based on the total weight of said blend. A polyol premix composition comprising:
a polyester polyol;
a halogenated olefin blowing agent;
and a distribution-enhancing component comprising at least one organic compound having from 1 to 40 carbon atoms, and the ability of said halogenated olefin blowing agent and said polyester polyol to form stable and substantially homogeneous compositions. A polyol premix composition, wherein said distribution reinforcing component is present in said polyol premix composition in a reinforcing effective amount. 9. The polyol premix composition of claim 8, wherein the distribution enhancing component has one or more hydroxyl groups and 1 to 25 carbon atoms. said distribution enhancing component comprises one or more of alcohols, glycols, ethers, acetals, benzenes, ketones, chlorinated solvents, carbonates, solvents, and surfactants;
9. The polyol premix composition of claim 8. 9. The polyol premix composition of claim 8, wherein said halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobut-2-ene. The distribution-enhancing component is present in an amount of at least 1.7% by weight of the polyol premix composition, ethanol, methanol, isopropanol, n-butanol, 2-propanol, 1-pentanol, 3-methyl-2- 12. The polyol premix composition of claim 11, comprising one or more of butanol and 2-methyl-1-propanol. The polyester polyol and any additional polyols are present in an amount from 50% to 98% by weight of the polyol premix composition, and the halogenated olefin blowing agent is present at 0.25% by weight of the polyol premix composition. % to 50% by weight, and the distribution enhancing component is present in an amount of 0.01% to 10% by weight of the polyol premix composition.
9. The polyol premix composition of claim 8, present in an amount of The polyester polyol and any additional polyols are present in an amount from 80% to 95% by weight of the polyol premix composition, and the halogenated olefin blowing agent is present at 0.25% by weight of the polyol premix composition. % to 10% by weight of the polyol premix composition, wherein the distribution enhancing component is present in an amount of 0.01% to 10% by weight of the polyol premix composition.
9. The polyol premix composition of claim 8, present in an amount of 9. The polyol premix composition of claim 8, wherein said stable, substantially homogeneous composition remains a substantially homogeneous mixture when stored under ambient conditions for a period of four months. A method of forming a polyol premix composition comprising:
Combining a polyester polyol, a halogenated olefin blowing agent, and a distribution enhancing component comprising at least one organic compound having from 1 to 40 carbon atoms to form a stable, substantially uniform composition wherein said distribution enhancing component is present in said polyol premix composition in an amount sufficient to enhance the performance of said halogenated olefin blowing agent and said polyester polyol. The distribution-enhancing components include alcohols, glycols, ethers, acetals, benzene, ketones, chlorinated solvents, carbonates, solvents, and surfactants, and the halogenated olefin blowing agents include cis-1,1,1, 17. The method of claim 16, comprising 4,4,4-hexafluorobut-2-ene. 17. The method of claim 16, wherein said stable, substantially homogeneous composition remains a substantially homogeneous mixture when stored under ambient conditions for a period of four months. A foamable composition comprising a mixture of an organic polyisocyanate and the polyol premix composition of claim 8. 20. The foamable composition of Claim 19, wherein the organic polyisocyanate comprises polymethylene polyphenyl isocyanate, methylene bis(phenyl isocyanate), toluene diisocyanate, or combinations thereof.